CN109750557A - A kind of preparation method of wear-resisting ventilative waterproofing agent for paper - Google Patents
A kind of preparation method of wear-resisting ventilative waterproofing agent for paper Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of wear-resisting ventilative waterproofing agent for paper, belong to papermaking treatments technical field.Polystyrene is first passed through sulfonation modifying by the present invention, to improve the dispersion performance of polystyrene in water, surface hydrophilic is made under the action of pore-foaming agent followed by the polystyrene after sulfonation modifying, the expanded polystyrene microballoon of inner hydrophobic, then by porous microsphere chloride obtained, and the porous microsphere after chloride is mixed with amino modified porous silica, to under the action of amido bond, modified porous silica is grafted on into expanded polystyrene microsphere surface, and then the surface of expanded polystyrene microballoon is made to form papillary structure, after being added in matrix resin together with modified lignin mahogany sulfonate, it is uniformly distributed among matrix resin, form flame-proof abrasion-resistant waterproofing agent for paper.Additive has excellent wearability in resulting product of the present invention, and internal containing hydrophobic through-hole, improves the wear-resisting permeability of product.
Description
Technical field
The invention discloses a kind of preparation methods of wear-resisting ventilative waterproofing agent for paper, belong to papermaking treatments technical field.
Background technique
Some speciality papers such as special packing paper, dispensable paper tableware paper products requires good waterproof performance.Tradition
Waterproof paper material be to cover one tunic of modeling in paper facer, and then make it have waterproofness, but this prevents paper products from complete
Portion's degradation causes environmental pollution, and also brings difficulty to later waste paper recovery processing and the utilization of secondary stock.Paper
The affinity for opening waterproofing agent and paper fibre is stronger, can reduce paper surface tension, has good waterproof performance, and environmental protection
It is degradable, thus be concerned by people.This project has synthesized a kind of hydrophobic acrylic resin's class waterproofing agent for paper, using table
The method of face sizing has carried out waterproof performance experiment, is studied the physical property of paper after sizing.
Isooctyl acrylate monomer, styrene etc. are that principal monomer is prepared for waterproofing agent for paper, utilize infrared spectroscopy and laser grain
Degree instrument characterizes synthetic polymer.Waterproofing agent dosage, retention agent dosage, beating degree, stop are had studied by plasm-glue-blending
The influence to paper waterproof performance such as time tests the waterproof performance of paper with osmosis and contact angle method, and to paper
Zhang Jinhang SEM electron microscope analysis.The result shows that paper has excellent waterproof performance.
Certain paper such as photographic paper, map paper, high-grade label paper, particular packing Paper or cardboard require height water resistant
Property, i.e., it is not spontaneously wet out by water or spreads, lasting, excellent " not getting wet " effect is presented.Hydrophobicity object need to be used by manufacturing this kind of paper
Matter is bonded to the surface of paper fibre or is impregnated into internal and fixed, and substance used is water repellent agent.Common water repellent agent has
Amino resins, Polyamide-Polyamsne-Epichlorohydrin, organosilicon etc..The water repellent agent of paper grade (stock) is mainly melamino-formaldehyde in recent years
Resin, this resinoid is and extremely unstable because containing formaldehyde, and easy gel need to use in acid condition, not meet Neutral Papermaking work
Skill requirement；Polyamide-Polyamsne-Epichlorohydrin, then because solid content is low, need to be cured under alkaline condition and be limited as water repellent agent
System.The main chain of organosilicon water repellent agent is Si-O key, and side chain is alkyl, is sprayed to paper surface, and polarity oxygen atom can be with
Polar group on fiber carries out hydrogen bond association, and the organic alkyl of nonpolarity is directed toward outside paper, paper surface formed one layer it is fine and close
Hydrophobic film is not spontaneously wet out by water or spreads to assign paper water-resistance, lasting, excellent " not getting wet " effect is presented；But by
It is more expensive in price, it is restricted its application.For specialties, the protection of such as precious calligraphy and painting but has certain Practical significance.
Silane coupling agent dodecyltrimethoxysilane is since alkyl is longer, so having preferable hydrophobic effect；Simultaneously because its phase
It is lower to molecular mass, it can penetrate into inside paper fibre, not block the gap of paper, so paper hydrophobicity can assigned
While, so that paper is kept normal gas permeability.So both materials are all likely to become new water resistant in terms of molecular structure
Agent.It is attempted for this this test.In view of that will not be generated greatly after the solvent volatilization in solvent type water repellent agent to water resistant effect
Influence；And if using emulsion-type, the selection of emulsifier just becomes the key of left and right water resistant effect, therefore this experiment choosing
Solvent type water repellent agent is selected.The compound of experiment amido silicon oil, dodecyltrimethoxysilane and the two is made into solvent type
Water repellent agent has investigated its water resistant effect to paper such as wrapping paper, paper for covering books, raw rice paper.
It take butyl acrylate, acrylic acid isooctyl, styrene etc. as the waterproofing agent for paper of principal monomer preparation, with polyethylene
Alcohol, cationic starch compounding prepare surface size and have carried out top sizing test, and with osmosis and contact angle method to paper
Waterproof performance tested, finally to paper carry out SEM electron microscope analysis.The result shows that: waterproofing agent dosage is 0.8%, polyethylene
Alcohol dosage is 2.0%, after surface size handling of paper of the cationic starch dosage for 1.5% compounding preparation, is shown excellent
Hydrophobic performance, while paper is resistance to broken.
Waterproofing agent for paper wear-resisting property and permeability traditional at present can not also further increase, and develop in the hope of exploring
Wear-resisting ventilative waterproofing agent for paper with good comprehensive performance is problem to be solved.
Summary of the invention
The present invention solves the technical problem of: traditional paper waterproofing agent wear-resisting property and permeability can not also be into one
The problem of step improves provides a kind of preparation method of wear-resisting ventilative waterproofing agent for paper.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of wear-resisting ventilative waterproofing agent for paper, it is specific the preparation method comprises the following steps:
(1) will pretreatment styrene mixed with dispersing agent 30:1~32:1 in mass ratio, and be added pre-process styrene quality 2~
3 times of initiator solution is stirred to react under nitrogen atmosphere, is filtered, dry, obtains polystyrene microsphere；
(2) polystyrene microsphere is mixed with concentrated sulfuric acid 1:10~1:11 in mass ratio, after being stirred to react, filters, wash, does
It is dry, obtain pretreatment polystyrene microsphere；
(3) pretreatment polystyrene microsphere is mixed with alcohol mixed solution 1:5~1:8 in mass ratio, after being stirred to react, mistake
Filter, it is dry, obtain pre- Modified polystyrene spheres；
(4) pre- Modified polystyrene spheres are mixed with thionyl chloride 1:8~1:15 in mass ratio, after back flow reaction, filters, does
It is dry, obtain Modified polystyrene spheres；
(5) Modified polystyrene spheres are mixed with modified manometer silicon dioxide 1.0:0.2~1.0:0.4 in mass ratio, and added
The ice water for entering 8~10 times of Modified polystyrene spheres quality after being stirred to react, filters, dry, obtains additive；
(6) modified sodium lignosulfonate solution is mixed with metal salt solution 1:2~1:3 in mass ratio, concentrated by rotary evaporation obtains modification
Lignosulfonates；
(7) matrix resin is mixed with additive 6:1~7:1 in mass ratio, and is added 0.1~0.2 times of matrix resin quality
Modified lignin mahogany sulfonate and 0.08~0.10 times of matrix resin quality of mixed initiator, after being stirred to react, obtain flame-proof abrasion-resistant
Waterproofing agent for paper.
Step (1) the pretreatment styrene is to mix styrene with sodium hydroxide solution 1:8~1:10 in mass ratio,
Distillation, obtains pretreatment styrene.
Step (1) initiator solution is to mix azodiisobutyronitrile with dehydrated alcohol 1:200 in mass ratio, step
(3) alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and 0.5~0.6 times of ethyl alcohol quality of positive heptan is added
Alkane after being stirred, obtains ethanol solution.
Step (5) modified manometer silicon dioxide is by polyethylene oxide-polypropylene oxide-polyethylene oxide three block
Copolymer is mixed with water 1:30 in mass ratio, obtains block copolymer dispersion liquid, and block copolymer dispersion liquid and concentrated hydrochloric acid are pressed body
Product is mixed than 4:1, and 0.25~0.30 times of block copolymer dispersion liquid volume of water is added, and after being stirred to react, must be pre-processed embedding
Section copolymer dispersion；Pretreatment block copolymer dispersion liquid is mixed with ethyl orthosilicate 25:1~30:1 in mass ratio, and
The 3- aminopropyl triethoxysilane of 0.01~0.02 times of block copolymer dispersion liquid quality of pretreatment is added, after being stirred to react,
It filters, washing obtains modified manometer silicon dioxide blank, modified manometer silicon dioxide blank is extracted in Soxhlet extractor, does
It is dry, obtain modified manometer silicon dioxide.
Step (6) the modified sodium lignosulfonate solution is by lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio
Mixing, and 1~4 times of formaldehyde quality of sodium sulfite is added, after being stirred to react under alkaline condition, obtain pretreatment lignin sulfonic acid
Pretreatment lignin sulfonic acid sodium solution is mixed with potassium iodide 90:1~100:1 in mass ratio, and pretreatment wood is added by sodium solution
1, the 6- dibromo-hexane solution of 0.2~0.3 times of quality sodium sulfonate solution quality, after being stirred to react under alkaline condition, must be handled
Agent composition, by processing agent composition extraction, filtering obtains filtrate, by filtrate concentrated by rotary evaporation, obtains modified sodium lignosulfonate；Institute
Stating 1,6- dibromo-hexane solution is to mix 1,6- dibromo-hexane with dehydrated alcohol 5:1 in mass ratio, and it is molten to obtain 1,6- dibromo-hexane
Liquid.
Step (7) described matrix resin is to mix butyl acrylate with Isooctyl acrylate monomer 2:1 in mass ratio, and be added
The styrene that 0.5 times of butyl acrylate quality, 0.1 times of butyl acrylate quality of methylacryoyloxyethyl triethyl methyl chlorine
Change ammonium and 2~3 times of butyl acrylate quality of water, after being stirred, obtains monomer dispersion liquid, monomer dispersion liquid and azo two is different
Fourth miaow hydrochloride 80:1 in mass ratio mixing, and 0.6~0.8 times of monomer dispersion liquid of water is added, it is stirred under nitrogen atmosphere anti-
Ying Hou obtains matrix resin.
Step (7) mixed initiator is to mix potassium peroxydisulfate with ammonium persulfate 3:1~4:1 in mass ratio, is obtained mixed
Close initiator.
Step (1) dispersing agent is to mix polyvinylpyrrolidone with hydroxypropyl cellulose 3:1 in mass ratio, score
Powder.
Step (6) metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio, and ferric trichloride is added
The copper chloride and 0.1~0.2 times of ferric trichloride quality of aluminium chloride that 0.1~0.3 times of quality, are stirred, obtain metal salt solution.
The beneficial effects of the present invention are:
(1) additive is added when preparing wear-resisting ventilative waterproofing agent for paper by the present invention, firstly, using pre- modified polyphenyl in additive
Ethylene microballoon, polystyrene microsphere is passing through pre- modified surface grafting sulfonate group, and is formed inside microballoon porous
Hydrophobic structure can improve the porosity of film after paper surface film forming in product, and then improve and produce after being added in product
The gas permeability of product, and due to the presence of pre- Modified polystyrene spheres sulfonic acid surfactant root, it can make additive after being added in product,
Products can be uniformly distributed in, and then further increase the gas permeability of product；Secondly, additive during the preparation process will be pre-
Modified polystyrene spheres chloride, and being mixed with modified porous silica, porous silica after modification,
Surface grafting has amino group, after mixing with the pre- Modified polystyrene spheres after chloride, can react, and form acyl
Amine key, so as in conjunction with pre- Modified polystyrene spheres, make nano silica in pre- modification modified porous silica
Surfaces of Polystyrene Microparticles forms nano-emulsion lug structure, and then further increases the hydrophobicity of additive, makes the waterproofness of product
It improves, also, since modified manometer silicon dioxide and pre- Modified polystyrene spheres are porous structure, after bonding,
It can guarantee the porosity of additive, and then improve the gas permeability of product, simultaneously as the presence of nano silica, in turn
The wear-resisting property of product can be made to improve；
(2) present invention is additionally added modified lignin mahogany sulfonate when preparing wear-resisting ventilative waterproofing agent for paper, on the one hand, sulfomethylated lignin
Hydrochlorate after modification, the metal ion in the adsorbable metal salt solution of sulfonate ion in lignosulfonates, thus
After being mixed with additive, modified lignin mahogany sulfonate can be adsorbed in additive under the suction-operated of improved silica
In additive surface, and modified lignosulfonates have three-dimensional net structure, can be by additive after product solidification
Stronger is fixed in product, reduces the loss of additive, and then improves the wear-resisting property of product, on the other hand, changes
Property after lignosulfonates one end there is hydrophobicity, after being adsorbed in around additive, additive and product surface can be made
Hydrophobicity further increases, so that the hydrophobicity of product is further increased, furthermore, lignosulfonates have more after modification
Good surface-active can promote additive being uniformly distributed in the product, and then keep the ventilative and wear-resisting property of product further
It improves.
Specific embodiment
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 30~50 DEG C, under conditions of revolving speed is 300~320r/min, after 1~5h of stirring and dissolving, obtains block copolymer dispersion
Liquid, 4:1 is mixed the hydrochloric acid for being 36~45% by block copolymer dispersion liquid and mass fraction by volume, and to block copolymer
In the mixture of dispersion liquid and concentrated hydrochloric acid be added 0.25~0.30 times of block copolymer dispersion liquid volume water, in temperature be 50~
55 DEG C, under conditions of revolving speed is 180~200r/min, after being stirred to react 4~6h, block copolymer dispersion liquid must be pre-processed；It will
Pretreatment block copolymer dispersion liquid mixed with ethyl orthosilicate 25:1~30:1 in mass ratio, and to pre-process block copolymer
The 3- ammonia of 0.01~0.02 times of block copolymer dispersion liquid quality of pretreatment is added in the mixture of dispersion liquid and ethyl orthosilicate
Propyl-triethoxysilicane is 40~50 DEG C in temperature, under conditions of revolving speed is 180~200r/min, is stirred to react 24~25h
Afterwards, it is 90~95 DEG C then at temperature, under conditions of revolving speed is 150~200r/min, after being stirred to react 45~48h, filters, obtain pre-
Modified manometer silicon dioxide blank is handled, after pretreatment modification nanometer titanium dioxide silicon blank is washed 1~3 time with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake obtains modified manometer silicon dioxide under conditions of being 80~90 DEG C in temperature by filter cake after dry 1~3h；By mass fraction
It is mixed in beaker for 10~12% lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio, and formaldehyde is added into beaker
Sodium hydroxide solution that the sodium sulfite that 1~4 times of quality is 5~10% with mass fraction adjust the pH of material in beaker be 10~
11, and be 90~95 DEG C in temperature, after revolving speed is stirred to react 2~3h under conditions of being 300~320r/min, it must pre-process wooden
Pretreatment lignin sulfonic acid sodium solution and potassium iodide 90:1~100:1 in mass ratio are mixed in three mouthfuls of burnings by plain sodium sulfonate solution
In bottle, and 1, the 6- dibromo-hexane of 0.2~0.3 times of sodium lignin sulfonate solution quality of addition pretreatment is molten into three-necked flask
Liquid controls the addition rate of 1,6- dibromo-hexane solution as 8~10mL/min, while the hydroxide for being 5~12% with mass fraction
The pH that sodium solution controls material in three-necked flask is 11.0~11.5, and is 80~85 DEG C in temperature, and revolving speed is 230~350r/
After being stirred to react 4~5h under conditions of min, obtain processing agent composition, will processing agent composition with after petroleum ether extraction 2~3 times,
Filtering, obtain filtrate, by filtrate in temperature be 60~80 DEG C, revolving speed be 120~180r/min, pressure be 500~600kPa item
Under part, concentrated by rotary evaporation to water content is 1~2%, obtains modified sodium lignosulfonate；Butyl acrylate and Isooctyl acrylate monomer are pressed
Mass ratio 2:1 is mixed in homogenizer, and 0.5 times of butyl acrylate quality of styrene, acrylic acid fourth are added into homogenizer
0.1 times of ester quality of methylacryoyloxyethyl triethyl methyl ammonium chloride and 2~3 times of butyl acrylate quality of water, Yu Wen
Degree is 50~60 DEG C, under conditions of revolving speed is 600~800r/min, after being stirred 20~50min, obtains monomer dispersion liquid, will
Monomer dispersion liquid and two isobutyl miaow hydrochloride 80:1 in mass ratio of azo are mixed in reaction kettle, and monomer is added into reaction kettle
The water that 0.6~0.8 times of dispersion liquid is passed through nitrogen into reaction kettle with the rate of 50~80mL/min, in temperature be 65~68 DEG C,
Under conditions of revolving speed is 200~350r/min, after being stirred to react 6~7h, matrix resin is obtained；It will pretreatment styrene and dispersing agent
The mixing of 30:1~32:1 in mass ratio pre-processes styrene quality 2 to being added in the mixture of pretreatment styrene and dispersing agent
~3 times of initiator solution, and be passed through into the mixture of pretreatment styrene and dispersing agent with the rate of 20~40mL/min
Nitrogen is 70~75 DEG C in temperature, under conditions of revolving speed is 300~320r/min, be stirred to react 20~for 24 hours after, filtering obtains poly-
Phenylethylene micro ball blank obtains polyphenyl second after being dried in vacuo 3~4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank
Alkene microballoon；Polystyrene microsphere is mixed with sulfuric acid 1:10~1:11 in mass ratio that mass fraction is 70~80%, is in temperature
40~50 DEG C, under conditions of revolving speed is 300~320r/min, after being stirred to react 6~8h, it is micro- must to pre-process polystyrene for filtering
Ball blank, after pretreatment polystyrene microsphere blank is washed with deionized 5~8 times, and the item for being 80~90 DEG C in temperature
Dry 1~3h, obtains pretreatment polystyrene microsphere under part；Polystyrene microsphere and alcohol mixed solution will be pre-processed in mass ratio
1:5~1:8 mixing, in temperature be 70~75 DEG C, revolving speed be 300~320r/min under conditions of, after being stirred to react 5~6h, mistake
Filter, obtains pre- Modified polystyrene spheres blank, vacuum under conditions of being 60 DEG C in temperature by pre- Modified polystyrene spheres blank
After dry 1~3h, pre- Modified polystyrene spheres are obtained；By pre- Modified polystyrene spheres and thionyl chloride 1:8 in mass ratio~
1:15 mixing, under conditions of being 60~80 DEG C in temperature after 5~8h of back flow reaction, filtering obtains Modified polystyrene spheres blank,
After being dried in vacuo 1~3h under conditions of being 60 DEG C in temperature by Modified polystyrene spheres blank, Modified polystyrene spheres are obtained；
Modified polystyrene spheres and modified manometer silicon dioxide 1.0:0.2~1.0:0.4 in mass ratio are mixed in amination pot, and
8~10 times of Modified polystyrene spheres quality of ice water is added into amination pot, is 70~72 DEG C in temperature, revolving speed is 300~
Under conditions of 320r/min, after being stirred to react 5~8h, filtering, obtain additive blank, by additive blank in temperature be 50~60
Under conditions of DEG C after dry 1~3h, additive is obtained；By modified sodium lignosulfonate solution and metal salt solution 1:2 in mass ratio
~1:3 mixing, in temperature be 30~50 DEG C, revolving speed be 250~320r/min under conditions of, after being stirred 1~2h, and in temperature
Degree is 60~80 DEG C, and revolving speed is 120~200r/min, and concentrated by rotary evaporation to moisture content is 1 under conditions of pressure is 500~600kPa
After~2%, modified lignin mahogany sulfonate is obtained；Matrix resin and additive 6:1~7:1 in mass ratio are mixed in blender, and
Into blender be added 0.1~0.2 times of matrix resin quality modified lignin mahogany sulfonate and matrix resin quality 0.08~
0.10 times of mixed initiator is 30~40 DEG C in temperature, under conditions of revolving speed is 300~320r/min, is stirred to react 2~3h
Afterwards, flame-proof abrasion-resistant waterproofing agent for paper is obtained.The pretreatment styrene be by styrene and sodium hydroxide solution 1:8 in mass ratio~
1:10 mixing, distillation obtain pretreatment styrene.The initiator solution be by azodiisobutyronitrile and dehydrated alcohol in mass ratio
1:200 mixing, obtains initiator solution.The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and ethyl alcohol is added
The normal heptane that 0.5~0.6 times of quality after being stirred, obtains ethanol solution.The mixed initiator is by potassium peroxydisulfate and over cure
Sour ammonium 3:1~4:1 in mass ratio mixing, obtains mixed initiator.The dispersing agent is that polyvinylpyrrolidone and hydroxypropyl is fine
Element 3:1 in mass ratio mixing is tieed up, dispersing agent is obtained.The metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio,
And 0.1~0.3 times of ferric trichloride quality of copper chloride and 0.1~0.2 times of ferric trichloride quality of aluminium chloride is added, stirring is mixed
It closes, obtains metal salt solution.
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 50 DEG C, under conditions of revolving speed is 320r/min, after stirring and dissolving 5h, block copolymer dispersion liquid is obtained, by block copolymerization
4:1 mix the hydrochloric acid that object dispersion liquid and mass fraction are 45% by volume, and mixing to block copolymer dispersion liquid and concentrated hydrochloric acid
Close and 0.30 times of block copolymer dispersion liquid volume of water be added in object, in temperature be 55 DEG C, under conditions of revolving speed is 200r/min,
After being stirred to react 6h, block copolymer dispersion liquid must be pre-processed；Pretreatment block copolymer dispersion liquid is pressed with ethyl orthosilicate
Mass ratio 30:1 mixing, and pretreatment block is added into the mixture of pretreatment block copolymer dispersion liquid and ethyl orthosilicate
0.02 times of copolymer dispersion quality of 3- aminopropyl triethoxysilane is 50 DEG C in temperature, and revolving speed is the item of 200r/min
It is 95 DEG C then at temperature after being stirred to react 25h under part, under conditions of revolving speed is 200r/min, after being stirred to react 48h, filters,
Pretreatment modification nanometer titanium dioxide silicon blank is obtained, after pretreatment modification nanometer titanium dioxide silicon blank is washed 3 times with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake after dry 3h, is obtained modified manometer silicon dioxide under the conditions of at a temperature of 90 °C by filter cake；It is 12% by mass fraction
Lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio are mixed in beaker, and 4 times of formaldehyde quality of Asia is added into beaker
The pH that the sodium hydroxide solution that sodium sulphate is 10% with mass fraction adjusts material in beaker is 11, and is 95 DEG C in temperature, is turned
After speed is stirred to react 3h under conditions of being 320r/min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid will be pre-processed
Sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask, and pretreatment sulfomethylated lignin is added into three-necked flask
0.3 times of acid sodium solution quality of 1,6- dibromo-hexane solution, the addition rate of control 1,6- dibromo-hexane solution are 10mL/min,
The pH of material is 11.5 in the sodium hydroxide solution control three-necked flask for being simultaneously 12% with mass fraction, and in temperature be 85 DEG C,
After revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether extraction 3 will be handled
After secondary, filtering, obtain filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min, pressure be 600kPa under conditions of, revolving
Being concentrated into water content is 2%, obtains modified sodium lignosulfonate；Butyl acrylate is mixed with Isooctyl acrylate monomer 2:1 in mass ratio
In homogenizer, and 0.5 times of butyl acrylate quality of styrene is added into homogenizer, 0.1 times of butyl acrylate quality
Methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality of water are 60 DEG C in temperature, and revolving speed is
Under conditions of 800r/min, after being stirred 50min, monomer dispersion liquid is obtained, by monomer dispersion liquid and two isobutyl miaow hydrochloric acid of azo
Salt 80:1 in mass ratio is mixed in reaction kettle, and 0.8 times of monomer dispersion liquid of water is added into reaction kettle, into reaction kettle with
The rate of 80mL/min is passed through nitrogen, is 68 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 7h, obtains base
Body resin；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to the mixture of pretreatment styrene and dispersing agent
Middle be added pre-processes 3 times of styrene quality of initiator solution, and into the mixture of pretreatment styrene and dispersing agent with
The rate of 40mL/min is passed through nitrogen, in temperature be 75 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react for 24 hours, mistake
Filter, obtains polystyrene microsphere blank, after being dried in vacuo 4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank, obtains poly-
Phenylethylene micro ball；The sulfuric acid 1:11 in mass ratio that polystyrene microsphere and mass fraction are 80% mix, in temperature be 50 DEG C,
Under conditions of revolving speed is 320r/min, after being stirred to react 8h, filtering must pre-process polystyrene microsphere blank, and pretreatment is poly-
After phenylethylene micro ball blank is washed with deionized 8 times, and the dry 3h under the conditions of at a temperature of 90 °C, polyphenyl second must be pre-processed
Alkene microballoon；Pretreatment polystyrene microsphere is mixed with alcohol mixed solution 1:8 in mass ratio, is 75 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 6h, filtering obtains pre- Modified polystyrene spheres blank, by pre- modified polystyrene
After microballoon blank is dried in vacuo 3h under conditions of being 60 DEG C in temperature, pre- Modified polystyrene spheres are obtained；By pre- modified polyphenyl second
Alkene microballoon is mixed with thionyl chloride 1:15 in mass ratio, and under conditions of being 80 DEG C in temperature after back flow reaction 8h, filtering obtains modification
Polystyrene microsphere blank must change after being dried in vacuo 3h under conditions of being 60 DEG C in temperature by Modified polystyrene spheres blank
Property polystyrene microsphere；Modified polystyrene spheres and modified manometer silicon dioxide 1.0:0.4 in mass ratio are mixed in amination
In pot, and 10 times of Modified polystyrene spheres quality of ice water is added into amination pot, in temperature be 72 DEG C, revolving speed 320r/
Under conditions of min, after being stirred to react 8h, filtering obtains additive blank, does under conditions of being 60 DEG C in temperature by additive blank
After dry 3h, additive is obtained；Modified sodium lignosulfonate solution is mixed with metal salt solution 1:3 in mass ratio, in temperature be 50
DEG C, it after being stirred 2h, and is 80 DEG C, revolving speed 200r/min in temperature, pressure is under conditions of revolving speed is 320r/min
After concentrated by rotary evaporation to moisture content is 2% under conditions of 600kPa, modified lignin mahogany sulfonate is obtained；Matrix resin and additive are pressed
Mass ratio 7:1 is mixed in blender, and into blender be added 0.2 times of matrix resin quality modified lignin mahogany sulfonate and
The mixed initiator that 0.10 times of matrix resin quality is 40 DEG C in temperature, under conditions of revolving speed is 320r/min, is stirred to react 3h
Afterwards, flame-proof abrasion-resistant waterproofing agent for paper is obtained.The pretreatment styrene is by styrene and sodium hydroxide solution 1:10 in mass ratio
Mixing, distillation, obtains pretreatment styrene.The initiator solution is by azodiisobutyronitrile and dehydrated alcohol in mass ratio 1:
200 mixing, obtain initiator solution.The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and ethyl alcohol matter is added
0.6 times of normal heptane after being stirred, obtains ethanol solution.The mixed initiator is that potassium peroxydisulfate and ammonium persulfate are pressed matter
Amount is mixed than 4:1, obtains mixed initiator.The dispersing agent is by polyvinylpyrrolidone and hydroxypropyl cellulose in mass ratio 3:
1 mixing, obtains dispersing agent.The metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio, and ferric trichloride is added
The copper chloride and 0.2 times of ferric trichloride quality of aluminium chloride that 0.3 times of quality, are stirred, obtain metal salt solution.
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 50 DEG C, under conditions of revolving speed is 320r/min, after stirring and dissolving 5h, block copolymer dispersion liquid is obtained, by block copolymerization
4:1 mix the hydrochloric acid that object dispersion liquid and mass fraction are 45% by volume, and mixing to block copolymer dispersion liquid and concentrated hydrochloric acid
Close and 0.30 times of block copolymer dispersion liquid volume of water be added in object, in temperature be 55 DEG C, under conditions of revolving speed is 200r/min,
After being stirred to react 6h, block copolymer dispersion liquid must be pre-processed；Pretreatment block copolymer dispersion liquid is pressed with ethyl orthosilicate
Mass ratio 30:1 mixing, and pretreatment block is added into the mixture of pretreatment block copolymer dispersion liquid and ethyl orthosilicate
0.02 times of copolymer dispersion quality of 3- aminopropyl triethoxysilane is 50 DEG C in temperature, and revolving speed is the item of 200r/min
It is 95 DEG C then at temperature after being stirred to react 25h under part, under conditions of revolving speed is 200r/min, after being stirred to react 48h, filters,
Pretreatment modification nanometer titanium dioxide silicon blank is obtained, after pretreatment modification nanometer titanium dioxide silicon blank is washed 3 times with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake after dry 3h, is obtained modified manometer silicon dioxide under the conditions of at a temperature of 90 °C by filter cake；It is 12% by mass fraction
Lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio are mixed in beaker, and 4 times of formaldehyde quality of Asia is added into beaker
The pH that the sodium hydroxide solution that sodium sulphate is 10% with mass fraction adjusts material in beaker is 11, and is 95 DEG C in temperature, is turned
After speed is stirred to react 3h under conditions of being 320r/min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid will be pre-processed
Sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask, and pretreatment sulfomethylated lignin is added into three-necked flask
0.3 times of acid sodium solution quality of 1,6- dibromo-hexane solution, the addition rate of control 1,6- dibromo-hexane solution are 10mL/min,
The pH of material is 11.5 in the sodium hydroxide solution control three-necked flask for being simultaneously 12% with mass fraction, and in temperature be 85 DEG C,
After revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether extraction 3 will be handled
After secondary, filtering, obtain filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min, pressure be 600kPa under conditions of, revolving
Being concentrated into water content is 2%, obtains modified sodium lignosulfonate；Butyl acrylate is mixed with Isooctyl acrylate monomer 2:1 in mass ratio
In homogenizer, and 0.5 times of butyl acrylate quality of styrene is added into homogenizer, 0.1 times of butyl acrylate quality
Methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality of water are 60 DEG C in temperature, and revolving speed is
Under conditions of 800r/min, after being stirred 50min, monomer dispersion liquid is obtained, by monomer dispersion liquid and two isobutyl miaow hydrochloric acid of azo
Salt 80:1 in mass ratio is mixed in reaction kettle, and 0.8 times of monomer dispersion liquid of water is added into reaction kettle, into reaction kettle with
The rate of 80mL/min is passed through nitrogen, is 68 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 7h, obtains base
Body resin；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to the mixture of pretreatment styrene and dispersing agent
Middle be added pre-processes 3 times of styrene quality of initiator solution, and into the mixture of pretreatment styrene and dispersing agent with
The rate of 40mL/min is passed through nitrogen, in temperature be 75 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react for 24 hours, mistake
Filter, obtains polystyrene microsphere blank, after being dried in vacuo 4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank, obtains poly-
Phenylethylene micro ball；Polystyrene microsphere is mixed with alcohol mixed solution 1:8 in mass ratio, is 75 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 6h, filtering obtains pre- Modified polystyrene spheres blank, by pre- modified polystyrene
After microballoon blank is dried in vacuo 3h under conditions of being 60 DEG C in temperature, pre- Modified polystyrene spheres are obtained；By pre- modified polyphenyl second
Alkene microballoon is mixed with thionyl chloride 1:15 in mass ratio, and under conditions of being 80 DEG C in temperature after back flow reaction 8h, filtering obtains modification
Polystyrene microsphere blank must change after being dried in vacuo 3h under conditions of being 60 DEG C in temperature by Modified polystyrene spheres blank
Property polystyrene microsphere；Modified polystyrene spheres and modified manometer silicon dioxide 1.0:0.4 in mass ratio are mixed in amination
In pot, and 10 times of Modified polystyrene spheres quality of ice water is added into amination pot, in temperature be 72 DEG C, revolving speed 320r/
Under conditions of min, after being stirred to react 8h, filtering obtains additive blank, does under conditions of being 60 DEG C in temperature by additive blank
After dry 3h, additive is obtained；Modified sodium lignosulfonate solution is mixed with metal salt solution 1:3 in mass ratio, in temperature be 50
DEG C, it after being stirred 2h, and is 80 DEG C, revolving speed 200r/min in temperature, pressure is under conditions of revolving speed is 320r/min
After concentrated by rotary evaporation to moisture content is 2% under conditions of 600kPa, modified lignin mahogany sulfonate is obtained；Matrix resin and additive are pressed
Mass ratio 7:1 is mixed in blender, and into blender be added 0.2 times of matrix resin quality modified lignin mahogany sulfonate and
The mixed initiator that 0.10 times of matrix resin quality is 40 DEG C in temperature, under conditions of revolving speed is 320r/min, is stirred to react 3h
Afterwards, flame-proof abrasion-resistant waterproofing agent for paper is obtained.The pretreatment styrene is by styrene and sodium hydroxide solution 1:10 in mass ratio
Mixing, distillation, obtains pretreatment styrene.The initiator solution is by azodiisobutyronitrile and dehydrated alcohol in mass ratio 1:
200 mixing, obtain initiator solution.The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and ethyl alcohol matter is added
0.6 times of normal heptane after being stirred, obtains ethanol solution.The mixed initiator is that potassium peroxydisulfate and ammonium persulfate are pressed matter
Amount is mixed than 4:1, obtains mixed initiator.The dispersing agent is by polyvinylpyrrolidone and hydroxypropyl cellulose in mass ratio 3:
1 mixing, obtains dispersing agent.The metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio, and ferric trichloride is added
The copper chloride and 0.2 times of ferric trichloride quality of aluminium chloride that 0.3 times of quality, are stirred, obtain metal salt solution.
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 50 DEG C, under conditions of revolving speed is 320r/min, after stirring and dissolving 5h, block copolymer dispersion liquid is obtained, by block copolymerization
4:1 mix the hydrochloric acid that object dispersion liquid and mass fraction are 45% by volume, and mixing to block copolymer dispersion liquid and concentrated hydrochloric acid
Close and 0.30 times of block copolymer dispersion liquid volume of water be added in object, in temperature be 55 DEG C, under conditions of revolving speed is 200r/min,
After being stirred to react 6h, block copolymer dispersion liquid must be pre-processed；Pretreatment block copolymer dispersion liquid is pressed with ethyl orthosilicate
Mass ratio 30:1 mixing, and pretreatment block is added into the mixture of pretreatment block copolymer dispersion liquid and ethyl orthosilicate
0.02 times of copolymer dispersion quality of 3- aminopropyl triethoxysilane is 50 DEG C in temperature, and revolving speed is the item of 200r/min
It is 95 DEG C then at temperature after being stirred to react 25h under part, under conditions of revolving speed is 200r/min, after being stirred to react 48h, filters,
Pretreatment modification nanometer titanium dioxide silicon blank is obtained, after pretreatment modification nanometer titanium dioxide silicon blank is washed 3 times with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake after dry 3h, is obtained modified manometer silicon dioxide under the conditions of at a temperature of 90 °C by filter cake；It is 12% by mass fraction
Lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio are mixed in beaker, and 4 times of formaldehyde quality of Asia is added into beaker
The pH that the sodium hydroxide solution that sodium sulphate is 10% with mass fraction adjusts material in beaker is 11, and is 95 DEG C in temperature, is turned
After speed is stirred to react 3h under conditions of being 320r/min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid will be pre-processed
Sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask, and pretreatment sulfomethylated lignin is added into three-necked flask
0.3 times of acid sodium solution quality of 1,6- dibromo-hexane solution, the addition rate of control 1,6- dibromo-hexane solution are 10mL/min,
The pH of material is 11.5 in the sodium hydroxide solution control three-necked flask for being simultaneously 12% with mass fraction, and in temperature be 85 DEG C,
After revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether extraction 3 will be handled
After secondary, filtering, obtain filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min, pressure be 600kPa under conditions of, revolving
Being concentrated into water content is 2%, obtains modified sodium lignosulfonate；Butyl acrylate is mixed with Isooctyl acrylate monomer 2:1 in mass ratio
In homogenizer, and 0.5 times of butyl acrylate quality of styrene is added into homogenizer, 0.1 times of butyl acrylate quality
Methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality of water are 60 DEG C in temperature, and revolving speed is
Under conditions of 800r/min, after being stirred 50min, monomer dispersion liquid is obtained, by monomer dispersion liquid and two isobutyl miaow hydrochloric acid of azo
Salt 80:1 in mass ratio is mixed in reaction kettle, and 0.8 times of monomer dispersion liquid of water is added into reaction kettle, into reaction kettle with
The rate of 80mL/min is passed through nitrogen, is 68 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 7h, obtains base
Body resin；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to the mixture of pretreatment styrene and dispersing agent
Middle be added pre-processes 3 times of styrene quality of initiator solution, and into the mixture of pretreatment styrene and dispersing agent with
The rate of 40mL/min is passed through nitrogen, in temperature be 75 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react for 24 hours, mistake
Filter, obtains polystyrene microsphere blank, after being dried in vacuo 4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank, obtains poly-
Phenylethylene micro ball；The sulfuric acid 1:11 in mass ratio that polystyrene microsphere and mass fraction are 80% mix, in temperature be 50 DEG C,
Under conditions of revolving speed is 320r/min, after being stirred to react 8h, filtering must pre-process polystyrene microsphere blank, and pretreatment is poly-
After phenylethylene micro ball blank is washed with deionized 8 times, and the dry 3h under the conditions of at a temperature of 90 °C, polyphenyl second must be pre-processed
Alkene microballoon；Pretreatment polystyrene microsphere is mixed with thionyl chloride 1:15 in mass ratio, is returned under conditions of being 80 DEG C in temperature
After stream reaction 8h, filtering obtains Modified polystyrene spheres blank, the item for being 60 DEG C in temperature by Modified polystyrene spheres blank
After being dried in vacuo 3h under part, Modified polystyrene spheres are obtained；Modified polystyrene spheres and modified manometer silicon dioxide are pressed into matter
Amount is mixed in amination pot than 1.0:0.4, and 10 times of Modified polystyrene spheres quality of ice water, Yu Wen are added into amination pot
Degree be 72 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 8h, filtering, obtain additive blank, by additive blank in
Temperature after dry 3h, obtains additive under conditions of being 60 DEG C；Modified sodium lignosulfonate solution and metal salt solution are pressed into quality
It is mixed than 1:3, is 50 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 2h, and is 80 DEG C in temperature, turns
Speed is that 200r/min obtains modified lignin mahogany sulfonate after concentrated by rotary evaporation to moisture content is 2% under conditions of pressure is 600kPa；It will
Matrix resin and additive 7:1 in mass ratio are mixed in blender, and 0.2 times of matrix resin quality is added into blender
Modified lignin mahogany sulfonate and 0.10 times of matrix resin quality of mixed initiator, in temperature be 40 DEG C, revolving speed 320r/min
Under conditions of, after being stirred to react 3h, obtain flame-proof abrasion-resistant waterproofing agent for paper.The pretreatment styrene is by styrene and hydroxide
Sodium solution 1:10 in mass ratio mixing, distillation obtain pretreatment styrene.The initiator solution is by azodiisobutyronitrile and nothing
Water-ethanol 1:200 in mass ratio mixing, obtains initiator solution.The alcohol mixed solution is by ethyl alcohol and water 1:1 in mass ratio
Mixing, and 0.6 times of ethyl alcohol matter of normal heptane is added, after being stirred, obtain ethanol solution.The mixed initiator is by persulfuric acid
Potassium is mixed with ammonium persulfate 4:1 in mass ratio, obtains mixed initiator.The dispersing agent is by polyvinylpyrrolidone and hydroxypropyl
Cellulose 3:1 in mass ratio mixing, obtains dispersing agent.The metal salt solution is to mix ferric trichloride and water 1:15 in mass ratio
It closes, and 0.3 times of ferric trichloride quality of copper chloride and 0.2 times of ferric trichloride quality of aluminium chloride is added, be stirred, obtain metal
Salting liquid.
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 50 DEG C, under conditions of revolving speed is 320r/min, after stirring and dissolving 5h, block copolymer dispersion liquid is obtained, by block copolymerization
4:1 mix the hydrochloric acid that object dispersion liquid and mass fraction are 45% by volume, and mixing to block copolymer dispersion liquid and concentrated hydrochloric acid
Close and 0.30 times of block copolymer dispersion liquid volume of water be added in object, in temperature be 55 DEG C, under conditions of revolving speed is 200r/min,
After being stirred to react 6h, block copolymer dispersion liquid must be pre-processed；Pretreatment block copolymer dispersion liquid is pressed with ethyl orthosilicate
Mass ratio 30:1 mixing, and pretreatment block is added into the mixture of pretreatment block copolymer dispersion liquid and ethyl orthosilicate
0.02 times of copolymer dispersion quality of 3- aminopropyl triethoxysilane is 50 DEG C in temperature, and revolving speed is the item of 200r/min
It is 95 DEG C then at temperature after being stirred to react 25h under part, under conditions of revolving speed is 200r/min, after being stirred to react 48h, filters,
Pretreatment modification nanometer titanium dioxide silicon blank is obtained, after pretreatment modification nanometer titanium dioxide silicon blank is washed 3 times with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake after dry 3h, is obtained modified manometer silicon dioxide under the conditions of at a temperature of 90 °C by filter cake；It is 12% by mass fraction
Lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio are mixed in beaker, and 4 times of formaldehyde quality of Asia is added into beaker
The pH that the sodium hydroxide solution that sodium sulphate is 10% with mass fraction adjusts material in beaker is 11, and is 95 DEG C in temperature, is turned
After speed is stirred to react 3h under conditions of being 320r/min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid will be pre-processed
Sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask, and pretreatment sulfomethylated lignin is added into three-necked flask
0.3 times of acid sodium solution quality of 1,6- dibromo-hexane solution, the addition rate of control 1,6- dibromo-hexane solution are 10mL/min,
The pH of material is 11.5 in the sodium hydroxide solution control three-necked flask for being simultaneously 12% with mass fraction, and in temperature be 85 DEG C,
After revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether extraction 3 will be handled
After secondary, filtering, obtain filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min, pressure be 600kPa under conditions of, revolving
Being concentrated into water content is 2%, obtains modified sodium lignosulfonate；Butyl acrylate is mixed with Isooctyl acrylate monomer 2:1 in mass ratio
In homogenizer, and 0.5 times of butyl acrylate quality of styrene is added into homogenizer, 0.1 times of butyl acrylate quality
Methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality of water are 60 DEG C in temperature, and revolving speed is
Under conditions of 800r/min, after being stirred 50min, monomer dispersion liquid is obtained, by monomer dispersion liquid and two isobutyl miaow hydrochloric acid of azo
Salt 80:1 in mass ratio is mixed in reaction kettle, and 0.8 times of monomer dispersion liquid of water is added into reaction kettle, into reaction kettle with
The rate of 80mL/min is passed through nitrogen, is 68 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 7h, obtains base
Body resin；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to the mixture of pretreatment styrene and dispersing agent
Middle be added pre-processes 3 times of styrene quality of initiator solution, and into the mixture of pretreatment styrene and dispersing agent with
The rate of 40mL/min is passed through nitrogen, in temperature be 75 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react for 24 hours, mistake
Filter, obtains polystyrene microsphere blank, after being dried in vacuo 4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank, obtains poly-
Phenylethylene micro ball；Polystyrene microsphere and modified manometer silicon dioxide 1.0:0.4 in mass ratio are mixed in amination pot, and to
10 times of polystyrene microsphere quality of ice water is added in amination pot, is 72 DEG C in temperature, under conditions of revolving speed is 320r/min, stirs
After mixing reaction 8h, filtering obtains additive blank, under conditions of being 60 DEG C in temperature by additive blank after dry 3h, must add
Agent；Modified sodium lignosulfonate solution is mixed with metal salt solution 1:3 in mass ratio, in temperature be 50 DEG C, revolving speed 320r/
It after being stirred 2h, and is 80 DEG C, revolving speed 200r/min in temperature, pressure is revolved under conditions of being 600kPa under conditions of min
Inspissation be reduced to moisture content be 2% after, obtain modified lignin mahogany sulfonate；Matrix resin is mixed in additive 7:1 in mass ratio and is stirred
It mixes in machine, and 0.2 times of matrix resin quality of modified lignin mahogany sulfonate and matrix resin quality 0.10 is added into blender
Mixed initiator again is 40 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred to react 3h, obtains flame-proof abrasion-resistant paper
Open waterproofing agent.The pretreatment styrene is to mix styrene with sodium hydroxide solution 1:10 in mass ratio, distills, obtains pre- place
Manage styrene.The initiator solution is to mix azodiisobutyronitrile with dehydrated alcohol 1:200 in mass ratio, and it is molten to obtain initiator
Liquid.The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and 0.6 times of ethyl alcohol matter of normal heptane is added, and is stirred
After mixing, ethanol solution is obtained.The mixed initiator is to mix potassium peroxydisulfate with ammonium persulfate 4:1 in mass ratio, must be mixed
Initiator.The dispersing agent is to mix polyvinylpyrrolidone with hydroxypropyl cellulose 3:1 in mass ratio, obtains dispersing agent.Institute
Stating metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio, and 0.3 times of ferric trichloride quality of copper chloride is added
With 0.2 times of aluminium chloride of ferric trichloride quality, it is stirred, obtains metal salt solution.
The lignin sulfonic acid sodium solution that mass fraction is 12% is mixed in beaker with formaldehyde 14:1 in mass ratio, and to
4 times of formaldehyde quality of sodium sulfite is added in beaker, adjusts material in beaker with the sodium hydroxide solution that mass fraction is 10%
PH is 11, and is 95 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 320r/min, obtains pretreatment sodium lignin sulfonate
Pretreatment lignin sulfonic acid sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask by solution, and are burnt to three mouthfuls
1, the 6- dibromo-hexane solution of 0.3 times of sodium lignin sulfonate solution quality of pretreatment is added in bottle, control 1,6- dibromo-hexane is molten
The addition rate of liquid is 10mL/min, while the sodium hydroxide solution for being 12% with mass fraction controls material in three-necked flask
PH is 11.5, and is 85 DEG C in temperature, after revolving speed is stirred to react 5h under conditions of being 350r/min, obtains processing agent composition, will
Agent composition is handled with after petroleum ether extraction 3 times, filtering obtains filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min,
Under conditions of pressure is 600kPa, concentrated by rotary evaporation to water content is 2%, obtains modified sodium lignosulfonate；By butyl acrylate and third
The different monooctyl ester of olefin(e) acid 2:1 in mass ratio is mixed in homogenizer, and 0.5 times of butyl acrylate quality of benzene second is added into homogenizer
Alkene, 0.1 times of butyl acrylate quality of methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality
Water is 60 DEG C in temperature, under conditions of revolving speed is 800r/min, after being stirred 50min, obtains monomer dispersion liquid, by monomer point
Dispersion liquid and two isobutyl miaow hydrochloride 80:1 in mass ratio of azo are mixed in reaction kettle, and monomer dispersion liquid is added into reaction kettle
0.8 times of water is passed through nitrogen into reaction kettle with the rate of 80mL/min, is 68 DEG C in temperature, revolving speed is the item of 350r/min
Under part, after being stirred to react 7h, matrix resin is obtained；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to pretreatment
It is added in the mixture of styrene and dispersing agent and pre-processes 3 times of styrene quality of initiator solution, and to pretreatment styrene
Nitrogen is passed through with the rate of 40mL/min with the mixture of dispersing agent, is 75 DEG C in temperature, revolving speed is the condition of 320r/min
Under, after being stirred to react for 24 hours, filtering obtains polystyrene microsphere blank, the condition for being 50 DEG C in temperature by polystyrene microsphere blank
After lower vacuum drying 4h, polystyrene microsphere is obtained；The sulfuric acid 1:11 in mass ratio for being 80% by polystyrene microsphere and mass fraction
Mixing is 50 DEG C in temperature, and under conditions of revolving speed is 320r/min, after being stirred to react 8h, it is micro- must to pre-process polystyrene for filtering
Ball blank, after pretreatment polystyrene microsphere blank is washed with deionized 8 times, and it is dry under the conditions of at a temperature of 90 °C
3h obtains pretreatment polystyrene microsphere；Pretreatment polystyrene microsphere is mixed with alcohol mixed solution 1:8 in mass ratio, in
Temperature is 75 DEG C, and under conditions of revolving speed is 320r/min, after being stirred to react 6h, filtering obtains pre- Modified polystyrene spheres blank,
After being dried in vacuo 3h under conditions of being 60 DEG C in temperature by pre- Modified polystyrene spheres blank, it is micro- to obtain pre- modified polystyrene
Ball；Pre- Modified polystyrene spheres are mixed with thionyl chloride 1:15 in mass ratio, are flowed back under conditions of being 80 DEG C in temperature anti-
After answering 8h, filtering obtains Modified polystyrene spheres blank, by Modified polystyrene spheres blank under conditions of temperature is 60 DEG C
After being dried in vacuo 3h, Modified polystyrene spheres are obtained；By Modified polystyrene spheres and nano silica in mass ratio 1.0:
0.4 is mixed in amination pot, and 10 times of Modified polystyrene spheres quality of ice water is added into amination pot, in temperature be 72
DEG C, under conditions of revolving speed is 320r/min, after being stirred to react 8h, filtering obtains additive blank, is in temperature by additive blank
Under conditions of 60 DEG C after dry 3h, additive is obtained；Modified sodium lignosulfonate solution and metal salt solution 1:3 in mass ratio are mixed
It closes, is 50 DEG C in temperature, after being stirred 2h, and is 80 DEG C in temperature, revolving speed is under conditions of revolving speed is 320r/min
200r/min obtains modified lignin mahogany sulfonate after concentrated by rotary evaporation to moisture content is 2% under conditions of pressure is 600kPa；By matrix
Resin and additive 7:1 in mass ratio are mixed in blender, and 0.2 times of matrix resin quality of modification is added into blender
Lignosulfonates and 0.10 times of matrix resin quality of mixed initiator are 40 DEG C in temperature, and revolving speed is the item of 320r/min
Under part, after being stirred to react 3h, flame-proof abrasion-resistant waterproofing agent for paper is obtained.The pretreatment styrene is that styrene is molten with sodium hydroxide
Liquid 1:10 in mass ratio mixing, distillation obtain pretreatment styrene.The initiator solution is by azodiisobutyronitrile and anhydrous second
Alcohol 1:200 in mass ratio mixing, obtains initiator solution.The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio,
And 0.6 times of ethyl alcohol matter of normal heptane is added, after being stirred, obtain ethanol solution.The mixed initiator be by potassium peroxydisulfate with
Ammonium persulfate 4:1 in mass ratio mixing, obtains mixed initiator.The dispersing agent is by polyvinylpyrrolidone and hydroxy propyl cellulose
Element 3:1 in mass ratio mixing, obtains dispersing agent.The metal salt solution be ferric trichloride is mixed with water 1:15 in mass ratio, and
0.3 times of ferric trichloride quality of copper chloride and 0.2 times of ferric trichloride quality of aluminium chloride is added, is stirred, it is molten to obtain metal salt
Liquid.
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is mixed with water 1:30 in mass ratio, in
Temperature is 50 DEG C, under conditions of revolving speed is 320r/min, after stirring and dissolving 5h, block copolymer dispersion liquid is obtained, by block copolymerization
4:1 mix the hydrochloric acid that object dispersion liquid and mass fraction are 45% by volume, and mixing to block copolymer dispersion liquid and concentrated hydrochloric acid
Close and 0.30 times of block copolymer dispersion liquid volume of water be added in object, in temperature be 55 DEG C, under conditions of revolving speed is 200r/min,
After being stirred to react 6h, block copolymer dispersion liquid must be pre-processed；Pretreatment block copolymer dispersion liquid is pressed with ethyl orthosilicate
Mass ratio 30:1 mixing, and pretreatment block is added into the mixture of pretreatment block copolymer dispersion liquid and ethyl orthosilicate
0.02 times of copolymer dispersion quality of 3- aminopropyl triethoxysilane is 50 DEG C in temperature, and revolving speed is the item of 200r/min
It is 95 DEG C then at temperature after being stirred to react 25h under part, under conditions of revolving speed is 200r/min, after being stirred to react 48h, filters,
Pretreatment modification nanometer titanium dioxide silicon blank is obtained, after pretreatment modification nanometer titanium dioxide silicon blank is washed 3 times with dehydrated alcohol,
Modified manometer silicon dioxide blank is obtained, after modified manometer silicon dioxide blank is extracted 48h in Soxhlet extractor, filtering is obtained
Filter cake after dry 3h, is obtained modified manometer silicon dioxide under the conditions of at a temperature of 90 °C by filter cake；It is 12% by mass fraction
Lignin sulfonic acid sodium solution and formaldehyde 14:1 in mass ratio are mixed in beaker, and 4 times of formaldehyde quality of Asia is added into beaker
The pH that the sodium hydroxide solution that sodium sulphate is 10% with mass fraction adjusts material in beaker is 11, and is 95 DEG C in temperature, is turned
After speed is stirred to react 3h under conditions of being 320r/min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid will be pre-processed
Sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask, and pretreatment sulfomethylated lignin is added into three-necked flask
0.3 times of acid sodium solution quality of 1,6- dibromo-hexane solution, the addition rate of control 1,6- dibromo-hexane solution are 10mL/min,
The pH of material is 11.5 in the sodium hydroxide solution control three-necked flask for being simultaneously 12% with mass fraction, and in temperature be 85 DEG C,
After revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether extraction 3 will be handled
After secondary, filtering, obtain filtrate, by filtrate in temperature be 80 DEG C, revolving speed 180r/min, pressure be 600kPa under conditions of, revolving
Being concentrated into water content is 2%, obtains modified sodium lignosulfonate；Butyl acrylate is mixed with Isooctyl acrylate monomer 2:1 in mass ratio
In homogenizer, and 0.5 times of butyl acrylate quality of styrene is added into homogenizer, 0.1 times of butyl acrylate quality
Methylacryoyloxyethyl triethyl methyl ammonium chloride and 3 times of butyl acrylate quality of water are 60 DEG C in temperature, and revolving speed is
Under conditions of 800r/min, after being stirred 50min, monomer dispersion liquid is obtained, by monomer dispersion liquid and two isobutyl miaow hydrochloric acid of azo
Salt 80:1 in mass ratio is mixed in reaction kettle, and 0.8 times of monomer dispersion liquid of water is added into reaction kettle, into reaction kettle with
The rate of 80mL/min is passed through nitrogen, is 68 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 7h, obtains base
Body resin；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio, to the mixture of pretreatment styrene and dispersing agent
Middle be added pre-processes 3 times of styrene quality of initiator solution, and into the mixture of pretreatment styrene and dispersing agent with
The rate of 40mL/min is passed through nitrogen, in temperature be 75 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react for 24 hours, mistake
Filter, obtains polystyrene microsphere blank, after being dried in vacuo 4h under conditions of being 50 DEG C in temperature by polystyrene microsphere blank, obtains poly-
Phenylethylene micro ball；The sulfuric acid 1:11 in mass ratio that polystyrene microsphere and mass fraction are 80% mix, in temperature be 50 DEG C,
Under conditions of revolving speed is 320r/min, after being stirred to react 8h, filtering must pre-process polystyrene microsphere blank, and pretreatment is poly-
After phenylethylene micro ball blank is washed with deionized 8 times, and the dry 3h under the conditions of at a temperature of 90 °C, polyphenyl second must be pre-processed
Alkene microballoon；Pretreatment polystyrene microsphere is mixed with alcohol mixed solution 1:8 in mass ratio, is 75 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 6h, filtering obtains pre- Modified polystyrene spheres blank, by pre- modified polystyrene
After microballoon blank is dried in vacuo 3h under conditions of being 60 DEG C in temperature, pre- Modified polystyrene spheres are obtained；By pre- modified polyphenyl second
Alkene microballoon is mixed with thionyl chloride 1:15 in mass ratio, and under conditions of being 80 DEG C in temperature after back flow reaction 8h, filtering obtains modification
Polystyrene microsphere blank must change after being dried in vacuo 3h under conditions of being 60 DEG C in temperature by Modified polystyrene spheres blank
Property polystyrene microsphere；Modified polystyrene spheres and modified manometer silicon dioxide 1.0:0.4 in mass ratio are mixed in amination
In pot, and 10 times of Modified polystyrene spheres quality of ice water is added into amination pot, in temperature be 72 DEG C, revolving speed 320r/
Under conditions of min, after being stirred to react 8h, filtering obtains additive blank, does under conditions of being 60 DEG C in temperature by additive blank
After dry 3h, additive is obtained；Matrix resin and additive 7:1 in mass ratio are mixed in blender, and are added into blender
The modified sodium lignosulfonate and 0.10 times of matrix resin quality of mixed initiator that 0.2 times of matrix resin quality be in temperature
40 DEG C, under conditions of revolving speed is 320r/min, after being stirred to react 3h, obtain flame-proof abrasion-resistant waterproofing agent for paper.The pretreatment benzene second
Alkene is to mix styrene with sodium hydroxide solution 1:10 in mass ratio, distills, obtains pretreatment styrene.The initiator solution
To mix azodiisobutyronitrile with dehydrated alcohol 1:200 in mass ratio, initiator solution is obtained.The alcohol mixed solution is will
Ethyl alcohol is mixed with water 1:1 in mass ratio, and 0.6 times of ethyl alcohol matter of normal heptane is added, and after being stirred, obtains ethanol solution.It is described
Mixed initiator is to mix potassium peroxydisulfate with ammonium persulfate 4:1 in mass ratio, obtains mixed initiator.The dispersing agent is that will gather
Vinylpyrrolidone is mixed with hydroxypropyl cellulose 3:1 in mass ratio, obtains dispersing agent.
Comparative example: the lignin sulfonic acid sodium solution that mass fraction is 12% is mixed in beaker with formaldehyde 14:1 in mass ratio
In, and 4 times of formaldehyde quality of sodium sulfite is added into beaker, beaker is adjusted with the sodium hydroxide solution that mass fraction is 10%
The pH of middle material is 11, and is 95 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 320r/min, must be pre-processed wooden
Pretreatment lignin sulfonic acid sodium solution and potassium iodide 100:1 in mass ratio are mixed in three-necked flask by plain sodium sulfonate solution, and
1, the 6- dibromo-hexane solution of 0.3 times of sodium lignin sulfonate solution quality of pretreatment is added into three-necked flask, controls 1,6- bis-
The addition rate of bromohexane solution is 10mL/min, while the sodium hydroxide solution for being 12% with mass fraction controls three-necked flask
The pH of interior material is 11.5, and is 85 DEG C in temperature, and after revolving speed is stirred to react 5h under conditions of being 350r/min, it is mixed to obtain inorganic agent
Close object, will processing agent composition with after petroleum ether extraction 3 times, filtering obtains filtrate, in temperature is 80 DEG C by filtrate, revolving speed is
180r/min, under conditions of pressure is 600kPa, concentrated by rotary evaporation to water content is 2%, obtains modified sodium lignosulfonate；By propylene
Acid butyl ester and Isooctyl acrylate monomer 2:1 in mass ratio are mixed in homogenizer, and butyl acrylate quality is added into homogenizer
0.5 times of styrene, 0.1 times of butyl acrylate quality of methylacryoyloxyethyl triethyl methyl ammonium chloride and acrylic acid fourth
The water that 3 times of ester quality is 60 DEG C in temperature, under conditions of revolving speed is 800r/min, after being stirred 50min, obtains monomer dispersion
Monomer dispersion liquid and two isobutyl miaow hydrochloride 80:1 in mass ratio of azo are mixed in reaction kettle by liquid, and are added into reaction kettle
The water for entering 0.8 times of monomer dispersion liquid, is passed through nitrogen into reaction kettle with the rate of 80mL/min, is 68 DEG C in temperature, revolving speed is
Under conditions of 350r/min, after being stirred to react 7h, matrix resin is obtained；Pretreatment styrene is mixed with dispersing agent 32:1 in mass ratio
It closes, pre-processes 3 times of styrene quality of initiator solution to being added in the mixture of pretreatment styrene and dispersing agent, and to pre-
Nitrogen is passed through with the rate of 40mL/min in the mixture of processing styrene and dispersing agent, in temperature be 75 DEG C, revolving speed 320r/
Under conditions of min, after being stirred to react for 24 hours, filtering obtains polystyrene microsphere blank, is in temperature by polystyrene microsphere blank
After being dried in vacuo 4h under conditions of 50 DEG C, polystyrene microsphere is obtained；In mass ratio by polystyrene microsphere and nano silica
1.0:0.4 is mixed in amination pot, and 10 times of polystyrene microsphere quality of ice water is added into amination pot, in temperature be 72
DEG C, under conditions of revolving speed is 320r/min, after being stirred to react 8h, filtering obtains additive blank, is in temperature by additive blank
Under conditions of 60 DEG C after dry 3h, additive is obtained；Matrix resin and additive 7:1 in mass ratio are mixed in blender, and
0.2 times of matrix resin quality of modified sodium lignosulfonate is added into blender and 0.10 times of matrix resin quality of mixing is drawn
Agent is sent out, is 40 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred to react 3h, obtains flame-proof abrasion-resistant waterproofing agent for paper.Institute
Stating pretreatment styrene is to mix styrene with sodium hydroxide solution 1:10 in mass ratio, distills, obtains pretreatment styrene.Institute
Stating initiator solution is to mix azodiisobutyronitrile with dehydrated alcohol 1:200 in mass ratio, obtains initiator solution.The ethyl alcohol
Mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and 0.6 times of ethyl alcohol matter of normal heptane is added, and after being stirred, obtains second
Alcoholic solution.The mixed initiator is to mix potassium peroxydisulfate with ammonium persulfate 4:1 in mass ratio, obtains mixed initiator.It is described
Dispersing agent is to mix polyvinylpyrrolidone with hydroxypropyl cellulose 3:1 in mass ratio, obtains dispersing agent.
Example 1 to the resulting wear-resisting waterproofing agent for paper of example 6 and comparative example product are subjected to performance detection, specific Air permenbility
Detection method is as follows: using the air permeability of YG46lE number air permeation volume gauge measurement test specimen handsheet, determination condition are as follows: pressure
13mmH2O, measurement circle towel Φ 50mm.
Wear-resisting property: it according to GB7911.7-87 standard method, is measured with III type paint film abrasion instrument of JM-.
Specific testing result is as shown in table 1:
The wear-resisting waterproofing agent for paper performance test results of table 1
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example |
| Air permenbility L/m2.s | 621.6 | 542.3 | 453.1 | 265.8 | 368.2 | 495.3 | 197.2 |
| Wear-resisting revolution/turn | 7800 | 7200 | 6500 | 7000 | 5260 | 2780 | 1560 |
By 1 testing result of table it is found that the wear-resisting waterproofing agent for paper of technical solution of the present invention preparation have excellent wear-resisting property and
The characteristics of permeability, has broad prospects in the development of papermaking treatments technology industry.
Claims (10)
1. a kind of preparation method of wear-resisting ventilative waterproofing agent for paper, which is characterized in that it is specific the preparation method comprises the following steps:
(1) will pretreatment styrene mixed with dispersing agent 30:1~32:1 in mass ratio, and be added pre-process styrene quality 2~
3 times of initiator solution is stirred to react under nitrogen atmosphere, is filtered, dry, obtains polystyrene microsphere；
(2) polystyrene microsphere is mixed with concentrated sulfuric acid 1:10~1:11 in mass ratio, after being stirred to react, filters, wash, does
It is dry, obtain pretreatment polystyrene microsphere；
(3) pretreatment polystyrene microsphere is mixed with alcohol mixed solution 1:5~1:8 in mass ratio, after being stirred to react, mistake
Filter, it is dry, obtain pre- Modified polystyrene spheres；
(4) pre- Modified polystyrene spheres are mixed with thionyl chloride 1:8~1:15 in mass ratio, after back flow reaction, filters, does
It is dry, obtain Modified polystyrene spheres；
(5) Modified polystyrene spheres are mixed with modified manometer silicon dioxide 1.0:0.2~1.0:0.4 in mass ratio, and added
The ice water for entering 8~10 times of Modified polystyrene spheres quality after being stirred to react, filters, dry, obtains additive；
(6) modified sodium lignosulfonate solution is mixed with metal salt solution 1:2~1:3 in mass ratio, concentrated by rotary evaporation obtains modification
Lignosulfonates；
(7) matrix resin is mixed with additive 6:1~7:1 in mass ratio, and is added 0.1~0.2 times of matrix resin quality
Modified lignin mahogany sulfonate and 0.08~0.10 times of matrix resin quality of mixed initiator, after being stirred to react, obtain flame-proof abrasion-resistant
Waterproofing agent for paper.
2. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (1)
The pretreatment styrene is to mix styrene with sodium hydroxide solution 1:8~1:10 in mass ratio, distills, obtains pretreatment benzene
Ethylene.
3. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (1)
The initiator solution is to mix azodiisobutyronitrile with dehydrated alcohol 1:200 in mass ratio, obtains initiator solution.
4. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (3)
The alcohol mixed solution is to mix ethyl alcohol with water 1:1 in mass ratio, and 0.5~0.6 times of ethyl alcohol quality of normal heptane is added,
After being stirred, ethanol solution is obtained.
5. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (5)
The modified manometer silicon dioxide is that polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and water are pressed matter
Amount is mixed than 1:30, obtains block copolymer dispersion liquid, and by block copolymer dispersion liquid, 4:1 is mixed by volume with concentrated hydrochloric acid, and
0.25~0.30 times of block copolymer dispersion liquid volume of water is added, after being stirred to react, block copolymer dispersion liquid must be pre-processed；
Pretreatment block copolymer dispersion liquid is mixed with ethyl orthosilicate 25:1~30:1 in mass ratio, and it is total that pretreatment block is added
The 3- aminopropyl triethoxysilane of 0.01~0.02 times of polymers dispersion liquid quality, after being stirred to react, filters, and washing obtains modification
Nanometer titanium dioxide silicon blank extracts modified manometer silicon dioxide blank in Soxhlet extractor, dry, obtains modified nano-silica
SiClx.
6. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (6)
The modified sodium lignosulfonate solution is to mix lignin sulfonic acid sodium solution with formaldehyde 14:1 in mass ratio, and formaldehyde is added
The sodium sulfite that 1~4 times of quality after being stirred to react under alkaline condition, must pre-process lignin sulfonic acid sodium solution, will pre-process
Lignin sulfonic acid sodium solution is mixed with potassium iodide 90:1~100:1 in mass ratio, and pretreatment lignin sulfonic acid sodium solution is added
0.2~0.3 times of quality of 1,6- dibromo-hexane solution, after being stirred to react under alkaline condition, obtains processing agent composition, will handle
Agent composition extraction, filtering obtain filtrate, by filtrate concentrated by rotary evaporation, obtain modified sodium lignosulfonate；The 1,6- dibromo-hexane is molten
Liquid is to mix 1,6- dibromo-hexane with dehydrated alcohol 5:1 in mass ratio, obtains 1,6- dibromo-hexane solution.
7. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (7)
Described matrix resin is to mix butyl acrylate with Isooctyl acrylate monomer 2:1 in mass ratio, and butyl acrylate quality is added
0.5 times of styrene, 0.1 times of butyl acrylate quality of methylacryoyloxyethyl triethyl methyl ammonium chloride and acrylic acid fourth
The water that 2~3 times of ester quality after being stirred, obtains monomer dispersion liquid, and monomer dispersion liquid and two isobutyl miaow hydrochloride of azo are pressed matter
Amount is mixed than 80:1, and 0.6~0.8 times of monomer dispersion liquid of water is added, and after being stirred to react under nitrogen atmosphere, obtains matrix tree
Rouge.
8. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (7)
The mixed initiator is to mix potassium peroxydisulfate with ammonium persulfate 3:1~4:1 in mass ratio, obtains mixed initiator.
9. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (1)
The dispersing agent is to mix polyvinylpyrrolidone with hydroxypropyl cellulose 3:1 in mass ratio, obtains dispersing agent.
10. the preparation method of the wear-resisting ventilative waterproofing agent for paper of one kind according to claim 1, it is characterised in that: step (6)
The metal salt solution is to mix ferric trichloride with water 1:15 in mass ratio, and be added 0.1~0.3 times of ferric trichloride quality
Copper chloride and 0.1~0.2 times of ferric trichloride quality of aluminium chloride, are stirred, obtain metal salt solution.
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| CN111877008A (en) * | 2019-03-02 | 2020-11-03 | 管伟 | Highly breathable superhydrophobic fibers |
| CN110172283A (en) * | 2019-05-30 | 2019-08-27 | 黄京合 | A kind of high transparency wear-resisting type floor paint |
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| CN113861356B (en) * | 2021-09-03 | 2024-04-16 | 浙江恒达新材料股份有限公司 | Modified lignin particle emulsion and preparation method and application thereof |
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